HCID 15163015, compound → HCID 67974858, compound

HRID 2169670Notes

Reaction equation

HRID 2169670 reaction equation
I[C:2]1[C:6](=[O:7])[S:5][C:4]2=[C:8](I)[C:9](=[O:11])[S:10][C:3]=12.C([Sn](CCCC)(CCCC)[C:18]1[S:19][CH:20]=[CH:21][C:22]=1[CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH3:30])CCC>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu](I)I.C1(C)C=CC=CC=1>[CH2:23]([C:22]1[CH:21]=[CH:20][S:19][C:18]=1[C:2]1[C:6](=[O:7])[S:5][C:4]2=[C:8]([C:18]3[S:19][CH:20]=[CH:21][C:22]=3[CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH3:30])[C:9](=[O:11])[S:10][C:3]=12)[CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH3:30]

Participants

6

Reactant 2

HCID 15163015HCID 15163015, compoundHCID 66653149HCID 66653149, compound

Product 1

HCID 67974858HCID 67974858, compoundYield 46.2%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

The 3,6-diiodo-thieno[3,2-b]thiophene-2,5-dione (1.000 g; 2.370 mmol), tributyl-(3-octyl-thiophen-2-yl)-stannane (Bras, Jérôme; Guillerez, Stéphane; Pépin-Donat, Brigitte. Chem. Mater. 2000, 12, 2372-2384) (2.977 g; 5.213 mmol), PdCl2(PPh3)2 (166 mg; 0.237 mmol), copper Iodide (45 mg; 0.237 mmol) and toluene (100 cm3) is added in a 250 cm3 flask. The resulting mixture is carefully degassed for 30 minutes, and then heated at 90° C. for 16 h under nitrogen protection. Silica is added and the solvent removed in vacuo. The crude product is purified by column chromatography (eluent: petroleum ether 40-60:DCM; 70:30 ratio) to recover the pure product as a red powder (612 mg, Yield: 46%). NMR (1H, 300 MHz, CDCl3): δ 7.47 (d, J=5.1 Hz, 2H); 7.02 (d, J=5.1 Hz, 2H); 2.57 (t, J=7.8 Hz, 4H); 1.61 (m, 4H); 1.26 (m, 20H); 0.86 (t, J=6.7 Hz, 6H). NMR (13C, 75 MHz, CDCl3): δ 186.92; 154.77; 145.82; 129.91; 192.26; 129.05; 123.79; 32.01; 30.70; 30.06; 29.61; 29.52; 29.37; 22.81; 14.27.

Workup

  1. customThe resulting mixture is carefully degassed for 30 minutes
  2. additionSilica is added
  3. customthe solvent removed in vacuo
  4. customThe crude product is purified by column chromatography (eluent: petroleum ether 40-60:DCM; 70:30 ratio)

Sources & evidence

ORD record
ord-4ba9f1003feb48e1a5707f496d1cfd0c
Source dataset
uspto-grants-2015_06
Patent number
US09048433B2

Reaction notes

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